WO2014080407A1 - Dithiocyanate de méthylène granulé, fluide et non poussiéreux - Google Patents

Dithiocyanate de méthylène granulé, fluide et non poussiéreux Download PDF

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Publication number
WO2014080407A1
WO2014080407A1 PCT/IL2013/050969 IL2013050969W WO2014080407A1 WO 2014080407 A1 WO2014080407 A1 WO 2014080407A1 IL 2013050969 W IL2013050969 W IL 2013050969W WO 2014080407 A1 WO2014080407 A1 WO 2014080407A1
Authority
WO
WIPO (PCT)
Prior art keywords
mbt
screw feeder
granulated
powder
feeder
Prior art date
Application number
PCT/IL2013/050969
Other languages
English (en)
Inventor
Shaul Shmilowitz
Xingye WU
Original Assignee
Bromine Compounds Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bromine Compounds Ltd. filed Critical Bromine Compounds Ltd.
Priority to JP2015543568A priority Critical patent/JP2016501860A/ja
Priority to US14/443,678 priority patent/US9326519B2/en
Publication of WO2014080407A1 publication Critical patent/WO2014080407A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/46—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=C=S groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/48—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —S—C≡N groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/22—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by pressing in moulds or between rollers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/02—Thiocyanates
    • C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to non-dusting solid forms of methylene dithiocyanate, a process for manufacturing them and their application.
  • Methylene dithiocyanate known also as methylene bis(thiocyanate)
  • MBT methylene bis(thiocyanate)
  • the applications of the material include water cooling systems, paint manufacturing, metalworking cutting fluids, pulp and paper mills, oil drilling/mud fluids, fracturing, leather processing, latex paints, wood pressure treatments, wood protection treatments - including as a wood preservative stain to combat wood rot in residential areas. Available are various formulations, comprising diluted liquids.
  • the MBT raw material is a powder solid under normal temperature, which is dusty and has tendency to cake.
  • MBT is highly toxic, and its potential degradation products include cyanide and formaldehyde; therefore, the dermal contact or inhalation should be particularly avoided. Therefore, a need is felt for a safe concentrated solid form, making the transport of raw MBT and its handling safer and cheaper. It is therefore an object of the invention to provide a solid concentrated MBT, which would be granular without employing a binder. It is a further object of this invention to provide a process for manufacturing a granular MBT without tendency to dust.
  • the invention provides granulated methylene bis(thiocyanate) (MBT) comprising at least 97% MBT in the form of granules having dimensions between 0.2 mm and 20 mm.
  • the granulated MBT according to the invention comprises particles having at least 87% of the MBT theoretical density.
  • the granulated MBT according to the invention is preferably a freely flowing and non-dusting solid, preferably without tendency to caking.
  • the invention is directed to a method of controlling or preventing an infestation by various pests, particularly microbial pests, comprising employing the granulated MBT consisting of at least 97% MBT within granules exhibiting dimensions between 0.2 mm and 20 mm.
  • the method according to the invention comprises employing said MBT in water cooling systems, in paint manufacturing, in metalworking cutting fluids, in pulp and paper mills, in oil & gas applications, fracturing, in drilling fluids, in leather processing, in latex paints, in wood protection treatments, and in wood pressure treatments.
  • Said controlling or preventing an infestation by pests comprises one of the following activities: bactericide, bacteriostatic, fungicide, fungistatic, algaecide, or algaestatic.
  • the invention provides a process for manufacturing granulated methylene bis(thiocyanate) (MBT) comprising at least 97% MBT in the form of granules exhibiting dimensions between 0.2 mm and 20 mm, comprising i) delivering a powder containing at least 97% MBT and no binder to a screw feeder of a pelletizer, for example by a vacuum feeder; and ii) compacting said powder by two rollers under the force of the screw feeder, wherein the delivery pressure is at least 500 kg/cm 2 and preferably at least 1000 kg/cm 2 .
  • MBT methylene bis(thiocyanate)
  • the process preferably comprises i) delivering a powder containing at least 97% MBT and no binder to a screw feeder of a pelletizer , for example by a vacuum feeder; ii) compacting said powder by two rollers, whereby obtaining a chunk, under the force of the screw feeder, wherein the delivery pressure is at least 1000 kg/cm 2 and preferably at least 1500 kg/cm 2 ; iii) crushing said chunk of MBT, whereby obtaining primary particles; and iv) screening said particles on a vibrating screen, whereby separating compacted MBT granules having dimensions of between 0.2 to 20 mm.
  • the process of the invention comprises i) delivering a powder containing at least 97% MBT and no binder to a screw feeder of a pelletizer by a vacuum feeder; ii) compacting said powder by two rollers, whereby obtaining a chunk, under the force of the screw feeder, wherein the delivery pressure is at least 1500 kg/cm 2 ; iii) crushing said chunk of MBT, whereby obtaining primary particles; iv) screening said particles on a vibrating screen, whereby separating final compacted MBT granules having dimensions of between 0.2 to 20 mm; and v) returning the remaining MBT material, not included in the final granules, to the screw feeder by vacuum feeder.
  • Said delivery pressure is up to 2500 kg/cm 2 .
  • the invention provides a process for manufacturing granulated methylene bis(thiocyanate) (MBT) exhibiting a density of at least 87% of the theoretical MBT solid density, comprising i) delivering a powder containing at least 97% MBT and no binder to a screw feeder of a pelletizer by a vacuum feeder; and ii) compacting said powder by two rollers under the force of the screw feeder, wherein the delivery pressure is at least 1500 kg/cm 2 ; iii) thereby obtaining a non-dusting solid MBT.
  • the process for manufacturing granulated methylene bis(thiocyanate) (MBT), the MBT exhibiting a density of at least 87% of the theoretical MBT solid density, for example at least 88% of the theoretical MBT solid density comprises i) delivering a powder containing at least 97% MBT and no binder to a screw feeder of a pelletizer by a vacuum feeder; and ii) compacting said powder by two rollers under the force of the screw feeder, wherein the delivery pressure is at least 1500 kg/cm 2 ; thereby obtaining a solid MBT with lower tendency to caking.
  • Methylene dithiocyanate can be compacted in a process of the invention without the addition of binders, fillers or any other additives.
  • the handling of the existing MBT solid material has required expensive safety precautions due to the hazardous nature of this biocide, especially in a fine powdered form; another problem in regard to the use of the available MBT solid material has been its tendency to create lumps, which has reduced the flowability and has caused handling and safety problems.
  • the present invention solves the mentioned problems.
  • the powdered MBT can be transformed to granulated MBT (assay 98% min.) by the dry process without using any binders, fillers or additives.
  • high quality granulated MBT is obtained under the delivery pressure of at least 500 kg/cm 2 , preferably at least 1000 kg/cm 2 , advantageously under the delivery pressure of at least 1500 kg/cm 2 of the rollers of the pelletizer.
  • This invention thus provides a method for preparing a safer form of MBT, which exhibits less dusting.
  • the form, granular MBT further exhibits lower tendency to aggregate to blocks and to cake.
  • the MBT product of the invention is safer for workers' health and for the environment; the product has improved flowability and improved potential to be applied as such or to be further processed in preparation of diluted formulations, solid or liquid.
  • the superior MBT form of the invention can be advantageously used in applications where dry dosing is needed, such as oil and gas drilling, mainly fracturing.
  • the instant invention provides MBT which is solid, concentrated, and easy to handle.
  • the MBT product consists of at least 97% methylene dithiocyanate, and lacks a binder.
  • Said product preferably comprises at least 98% MBT, and is in a form comprising pellets, granules tablets or briquettes.
  • Methylene dithiocyanate (MBT) in the form according to the invention will advantageously be used for controlling bacteria, algae, yeasts and fungi, for example in industrial water systems. Other applications include, for example, wood and leather preservation.
  • MBT according to the invention will be also advantageously used in preparing formulations in organic solvents or as aqueous dispersions. Excellent penetrating powers of this pesticide makes it a preferred biocide in many applications, but the advantageous form of the invention will broaden its applications.
  • the technology of the invention can essentially yield a pure granulated MBT product, and in a preferred embodiment, the product is manufactured while comprising a pelletizer (compacting machine) without adding any binders, fillers or additives, which ensures that the use of the product will not be adversely affected by lowering the concentration of the active agent.
  • the technology of the invention can yield the dried pure granulated MBT, and the shape of the granules may be modified within the ambit of the present technology. Various shapes may be demanded in the market and they are obtainable from a pelletizer or a compacting machine within the scope of the invention.
  • Both compaction granules and briquettes are made with a roll press. In one aspect, the compaction granules are made from loose material that has been compacted together (forming a chunk) and then broken apart, possibly in a granulator. In another aspect, briquettes or tablets are formed.
  • a method of reducing pests comprising the use of granulated MBT of the invention, wherein the pests comprise at least one of viruses, bacteria, anaerobic bacteria, sulfate reducing bacteria, sulfide-producing bacteria, slime-forming bacteria, algae, fungi, fungi associated with sapstain or dry rot, surface mold, spoilage microorganisms, yeast, and parasites.
  • dusting raw material is compacted to particles of at least 87% of the MBT theoretical density.
  • the granular MBT exhibits a density of at least 88% of the theoretical density.
  • the granular MBT has a density corresponding to from 87 to 89% of the theoretical density.
  • the MBT granulated product of the invention will advantageously be incorporated directly, or after dissolving, or after dispersing, into products such as adhesives, coatings, fuels, metalworking cutting fluids, plastic products, resin emulsions, paints, paper products, oil & gas applications, fracturing and other industrial products.
  • pelletizing may be done in a pellet mill, where feed is conditioned and thermally treated in the fitted conditioners of a pellet mill, the feed then being pushed through the holes and a pellet die, and exits the pellet mill as pelleted feed.
  • dry granulation process aggregates the primary powder particles under high pressure, producing either a large tablet (slug) in a heavy duty tabletting press or, alternatively, the powder is squeezed between two rollers (roller compactor, chilsonator) to produce a sheet of squeezed material.
  • granules are formed by the addition of a liquid onto a powder bed which is under the influence of an impeller (in a high shear granulator), screws (in a twin screw granulator) or air (in a fluidized bed granulator).
  • an impeller in a high shear granulator
  • screws in a twin screw granulator
  • air in a fluidized bed granulator
  • the granular MBT of the invention may be obtained from various powders, when compacting under the delivery pressure of preferably more than 500 kg/cm 2 , and still more preferably more than 1000 kg/cm 2 , for example of about 1500 kg/cm 2 , of the rollers of a pelletizer, possibly providing a chunk to be crushed and sieved. Higher compression, and bringing the granule density closer to the theoretical density (about 0.82) will provide higher granule stability.
  • MBT is compacted in accordance with the drawing and/or as described below.
  • High quality granulated MBT can be obtained when compacting under the delivery pressure of no less than 1500 kg/cm 2 of the rollers of a pelletizer, wherein the main steps include:
  • the MBT powder is compacted to a chunk by two rollers under the force of the screw feeder;
  • the chunk of MBT goes down to a crusher for crushing, whereby the MBT is crushed into mixture of greater particles and finer powder, and then the mixture goes through the vibration sieve, by which the particles of MBT are separated and collected;
  • the pelletizer is preferably covered by an airproof frame, and the MBT powder is fed to the pelletizer through air-tight PP lines, avoiding dust escape to the open air.
  • the end of the vacuum feeder and the airtight frame are preferably connected to the bag house via cyclone separator, and then to the scrubbing column.
  • the bag house is cleaned periodically for MBT recovering; the absorption liquid in the column may be water, and MBT can be recovered to lower the costs and increase the yield.
  • the MBT production according to the invention thus, being a safe for human health and environmentally friendly.
  • rollers (kg/cm 2 ) (g/cm 3 ) (mm) (mm) (mg)
  • the production of the granulated MBT was performed by processing 500 kg powder containing about 98.5% MBT, the diameter of the holes of the crushing screen was 8 mm, the delivery pressure being 1500 kg/cm 2 .
  • the granulated MBT product was obtained without any aid of binders, fillers or additives, yielding 490 kg of 4-12 mm high quality granules of MBT obtained.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Glanulating (AREA)
  • Toxicology (AREA)

Abstract

L'invention concerne du dithiocyanate de méthylène granulé pour une utilisation antimicrobienne industrielle sûre et sans danger pour l'environnement, et un procédé pour sa fabrication.
PCT/IL2013/050969 2012-11-26 2013-11-25 Dithiocyanate de méthylène granulé, fluide et non poussiéreux WO2014080407A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2015543568A JP2016501860A (ja) 2012-11-26 2013-11-25 流動性を有する無粉塵性の粒状メチレンジチオシアナート
US14/443,678 US9326519B2 (en) 2012-11-26 2013-11-25 Flowable and non-dusting granulated methylene dithiocyanate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261729753P 2012-11-26 2012-11-26
US61/729,753 2012-11-26

Publications (1)

Publication Number Publication Date
WO2014080407A1 true WO2014080407A1 (fr) 2014-05-30

Family

ID=50775641

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL2013/050969 WO2014080407A1 (fr) 2012-11-26 2013-11-25 Dithiocyanate de méthylène granulé, fluide et non poussiéreux

Country Status (3)

Country Link
US (1) US9326519B2 (fr)
JP (1) JP2016501860A (fr)
WO (1) WO2014080407A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108905894B (zh) * 2018-06-13 2021-03-09 武汉科技大学 一种自动脱模干粉造粒机

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849134A (en) * 1985-11-13 1989-07-18 Bromine Compounds Limited Granular flame retardant agents and process for their preparation
CN1080234A (zh) * 1993-03-19 1994-01-05 达式宪 将粉状燃料压制成有孔颗粒状的成型机

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8906234D0 (en) * 1989-03-17 1989-05-04 Albright & Wilson Agrochemical suspensions
US6281169B1 (en) * 1999-07-29 2001-08-28 Biolab Services, Inc. Aqueous suspensions of low solubility and low stability water additives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849134A (en) * 1985-11-13 1989-07-18 Bromine Compounds Limited Granular flame retardant agents and process for their preparation
CN1080234A (zh) * 1993-03-19 1994-01-05 达式宪 将粉状燃料压制成有孔颗粒状的成型机

Also Published As

Publication number Publication date
US20150282485A1 (en) 2015-10-08
JP2016501860A (ja) 2016-01-21
US9326519B2 (en) 2016-05-03

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